Process of producing fast dyeings and the dyed fiber obtained thereby



Patented July 4, 1944 UNITED STATES" PATENT OFFICE PROCESS PRODUCING FAS T DYEINGS AND THE DYED FIBER OBTAINED ErichFischer, Bad Soden' in Taunus, Werner Kirst, Konigstein in Taunus, and Walter Gmelln, Bad Soden in TaunusPGermany, assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Delaware N Drawing. Application November 27, 1940, Se-

rial No. 367,37 1939.

The present invention relates to a processof producing fast dyeings on animal fibers and cellulose fibers as well as on mixtures of animal fibers with cellulose fibers, furthermore oll structures from synthetic polyamides of high molecular weight, and to the dyedfiber obtained there- We have found that valuable dyeings of good properties of fastness can be obtained onanimal ,Werner Kirst, Carl JosefMueller, and Willy Schumacher, for Process of producing fast dyepound of the aromatic or heterocyclic' series containing imthe molecule an amino-group capable of being diazotized, then diazotizing and developing the dyestufi by means of an alkaline treatment. I It is surprising that the fastness to wetp-rocessing of the dyeings, particularly their fastrless to water, to perspiration, to washing, to fulling and to potting is essentially improved by the after-treatment with an agent ,yielding metal, sincethe dyestufis produced on the fiber do'not containthe known configurations capable of iorming'a metal complex compound, such as, for

,instance, the salicylic acid grouping olthe rouping:

V n H I I wherein x stands for on, COOH, run or 0on5.

The said improvement in the properties of fastness is obtained on animal fibers aswell as on cellulose fibers, and in general the shade is not so much displaced as is usually observed when metal complex compounds are formed.

I The treatment with the agents yielding metal may be performed in the presence of organic dispersing agents, whereby the fastnessto rubbing of thadyeings is in many cases improved.

In Germany February 16,

11 Claims. (01. 8-22) Serial No. 221,715, filed July 28,1938, in the 'name of Werner Kirst, i'orfProcess of'producing fast dyelngs and the dyed fiber obtained the U. S. patent application Serial No. 261,378, filed March 11, 19 39, in the name or Georg Kraenzlein,

lugs and the dyed fiber obtained thereby? As agents yielding metal there may. for' instance, be used chromiumsalts, such as chromiuln fluoride, chromium sulfate, chromium acetate, potassium bichromate; copper salts, such as copper sulfate; cobalt salts, such as cobalt ni trate, cobalt sulfate, cobaltous chloride; nickel salts, such as nickel sulfate; aluminium salts,

such as aluminium acetate; iron salts, such as ferric sulfate; manganese salts, such as manganous chloride, manganesenitrate, manganese sulfate; furthermore, cadmium sulfate. uranium nitrate, vanadium chloride, strontium chloride -and the'like. 1' 1 The following examples serve to illustrate the invention. but they'are not. intended to limit it thereto:

1. 1 kilo of mixed yarn consisting of 50 parts of wool and 50 parts of staple fiber from viscose is treated for '1 hour at 95 C. in 24 liters of water containing 50 grams of the dyestufi 1-amino-5- hydroxynaphthalene 7 sulfonic acid- Cleves acid- 2 amino-8-hydroxynaphthalene 6 sulfonic acid and '80 grams of ammonium sulfate.

600 grams-of sodium sulfate, dissolved in 6 liters of .water; are then added and the material is further treated for half an hour at a temperature falling to 80 C. It is then rinsed,"dlazotized for half an'hour in the cold in a bath containing per '30 liters of water 25 grams of sodium nitrite, 12

, grams ofsodium d'ibutyinaphthalene-sulfonate The dyestuffs used as parent materials in the and '75 cc. of hydrochloric acid of 20 B., andde-' veloped for half an hour in a solution containing I per 30 liters---of..coldwater cc. of ammonia of 25 percent. strength and 10 grams of the condensation product from-'1 moi of octodecylalcohol and 20 mols of ethylene oxide. The material is thenrinsed and treated for /4 to 1 hour at 95 C. in a bath containing per 30 liters of water 20 grams 'of potassium-bichromate, 20 cc. of formic acid of per cent. strength and 5 grams of the condensation product from-Lmol of octodecylalcohol and 20 mols of ethylene oxide. 3 The ,black dyeing thuspbtained has practically the same shade as the dyeing produced without aftr-treatmelrtwith a metal salt. The fastness to water, to perspiration, to washing, .to potting and to fulling is essentially improved.

The dyeings developed by a treatment with chromium fluoride, chromium sulfate, chromium acetate, copper sulfate, cobaltX nitrate, cobalt sulfate, aluminium acetate, manganous chloride, nickel sulfate, vanadium chloride, uranium nitrate, strontium chloride and acetic acid like wise show a considerable; improvement in their fastness to wet-processing. I I,

2. 1 kilo of mix ed yarn consisting of 50 parts or wool and 50 parts of staple fiber from viscose is treated for /4 hourat 90 C. in 30 liters of water containing 40 grams of the dyestuff lamino 5 hydroxynaphthalene-7-sulfonic acid Cleves acid- Cleves acid, 40 grams 0! amm'onium sulfate and 600 grams of sodium suliate,-

and the material is further treated for hour at a temperature falling to 75 C. It is then .rinsed, diazotized as described in Example 1, and the' dyestufi is developed to a dark-brown dyeing in an ammoniacal bath and rinsed again. The dyeing thus obtained is treated for 1. hour .at 90 C. in a solution containing per 30 liters 600 grams oifsodium sulfate.

of water 20 .grams of chromium fluoride and 20 cc. of acetic acid of 50 per cent. strength, rinsed and dried.

The brown-dyeing thus obtained is essentially faster to water, to perspiration and to washing than the dyeing produced withouttreatment with an agent yielding metal.

3. 1 kilo of mixed yarn consisting, of 50 parts of wool. and 50 parts of staple fiber from cuprammonium cellulose is treated for 1 hour at '15- C. in 24 liters of water containing 40 grams of the dyestufl obtainable by coupling diazotized 1-ainino-3-chloro-4-nitrobenzene with 2-amino-..

5-hydroxynaphthalene-'7-sulfonic acid, in an acid medium, and subsequently reducing the fate. 600 grams of sodium sulfate; dissolved in 6 liters of cold water, are then added and the finaterialis further treated for half an hour at 60 C. veloped by means of ammonia, as described in Example 1, rinsed again and after-treated for one hour at 90 C. in a bath containing per 30 liters of water 20 grams of potassium bichromateand 20 cc. of acetic acid of 50 percent. strength; The fastness to water, to perspiration, to washing and to potting of the dyeing after-treated with the chromium salt is essentially better than that of the dyeing which has not been aftertreated.

It is then rinsed, diazotized and 'de-' wool and 50 parts of staple fiber from viscose containing effects from acetate artificial silk is treated at 90 C. in a bath containing per liters! water 1 #40 grams of the dyestui! 4,4'- diaminodiphenyl- 2,2 -disulfonic acid- 1 -(3'- aminophenyD- 5 pyrazolone-ii-carboxylic acid, 0..5 gram of the dyestufl diaminotriphenylmethane=:1-(4'-sulfophenyl)-3 -methyl; 5 -pyrazolone,

' 1 gram of thedyestufl:

H1 H3 NH:

6,841 01110 Mid NH:

10' grams of the condensation product from'l 7 mol. of'octodecylalcohol and 20 mole of ethylene'oxide, 40 gramfoi ammonium sulfate and The material is then allowed to stand for /4 I hour at a temperature falling to C.. rinsed. and treated for half an hour in the cold a bath containing a 25 grams of sodium nitrite,

10 grams of sodium dibutylnaphthalenesulionate and a '15 cc. of hydrochloric acid 01 20 B in 30 liters of cold water, and developed for halt ,an hour in a solution containingper 30 liters of cold water a cc. of ammonia or 25 per cent strength and I 5 grams or the condensation product from 1- mol ,nitro-group, and 50 grams or ammonium sulof octodecylalcohol and '20 mols of ethylene oxide. Y

The material is then treated for 1 hour at C.

ina bath containing per 30 liters of water 20 grams of 'chromium'fluoride,

10 grams of glacial acetic acidand 5 grams of the condensation product'oi' l-mol I ,of octodecylalcohol and '20 ,mols of'ethylene oxide,

rinsed and dried. A yellow dyeing of very good 1 properties of fastness is obtained. The eil'ecta from acetate artificial silk remainqvhite.

The following table illustrates the shades of a number of other dyeings obtainable by the present invention: I i

c. 1 kilo of a fabric 'consistingof so was of Parent component sum 0! the dyeing, treated with new 1 IIIULOH mixtures o wool snd artificial till it ber .Hots

- Treated with ooppor sulfate: subdued red. I

Treated with copper mum: yellow-brown.

:: 2-bydrox nap'hthalene- Parent component Shade oi the dyeing, treated with metal salts on mixtures of wool and artificial silk stapie fiber H018 NH: 7

3"-aminohenzoyi-3-aminobenzoyl-2-amino-5-hydroxynaphthalene-7-sulionic acid 1-(3-amiuophenyi)-5-pyrazolone-3-carboxylic acid.

1amino-5-hydroxynaphthaleueJ-suifonic acid Cleve's acid 2-amin0-5- hydroxynaphthalene-7-sulfonic acid. V l-anliino -5-h groxynaphthalene-7-su1fouic acid 0 1-amino-2,5-dimethylbeuzeue eve s aci 2-amino-5-hydroxynaphthalene-7-sullonic acid Cieve's acid hydroxynaphthalene-7-suliouie acid. Z-auiino-5-hydroxynaphthalene-7-suiiouic 801d -o Cleve's acid v 2-amlno-8- hydroxyuaphthaleue-G-suifonicac H l alkaline l-amlno-7-hydroxynaphthalene-3-sulfouic acid ;4 l-naphthylamine 1-amino-5- hydroxynaphthaierie-7-suiionic acid. 2-agliino-8-hsigroxynaphthalene e-sulionic acid 0 1-amino-3,5-dimethylben;zene

eve'sac l-amino-5-hydroxynaphthaiene-7-sulionic acid a Cleve'sacid -o Cleves acid...

Ha H:

(obtainable by coupling diazotized i-nitranlline with the tgs'r'azolone iii-om the hydrazine oi the dehydrothiotoluidine sulfonic acid, and reducing a nitl'o-Iro D) Treated with potassium bichromate: redbrown.

Treated with copper sulfate: brown-orange.

Treated with potassium hichromate: red.

Treated with potassium bichromate; subdued orange.

' Treated with potassium bichromate: brown Trglzttggl with potassium bichromate: blue- Treatcd with chromium fluoride: brown.

Treated with potassium bichromate: black.

Treated with potassium bichromate: yellowh-red.

Treated with chromium fluoride: dark-blue. Treated with copper sulfate: dark-brown.

Treated with chromium fluoride: violethrown.

Treated .with potassium hichromate: copperbrown.

Treated with copper uliatei brown.

Treated with potassium bichromate: dull Tr e t d with eoppersuliate: brown-orange.

Do. I

Treated with chromium fluoride: blue-black.

Treated with chromium fluoride: subdued orange.

PBI'BD Q component Shade oi the dyeing, treated with metal salts on mixtures of wool and artificial lllk staple fiber NH: on NHT 3N=NJQ=BL2 p egm 0:11 SOIK S 3 ii I NH (obtainable by coupling 2 mols oi diazotized a-nitraniline with the bisgyrazolone from the hydrazine or 4,4'4.iamino-stllbene-2,2disulionic acid, and reducing t e nitro roups).

(obtainable by coupling diazotlzed dehydrothlotoluldlnesulionic acid with l-(3'-aminophcuyl F-5-pyrazolone-3-oarboxylic acid).

(obtainable by coupling diazotized 4'-nitrobenzoyl-l.4d iaminobenzene-t -sulfonic acid with l-(3-aminophenyl)-3-methyl-5-pyrazolone and reducing the nitro-group).

l-(3'-ominobenzoyiarnino)-3-aminobenzene:: 2 mols oi i-(3-nitrophenyl)-5-pyrazoione- -3-carboxylic acid and reduction of the ultra-groups).

i-(4'-nitrobenzoyiamiuo)-4-amiuobenzene l-phenylgzlrazolone-carboxyiic acid,

reduced 4-arninobenzoyl-2-amino'-5 hydroxynapht eue-7-suliouic ac d.

NH, -0 2,4-diaminotoluene-5-suliouic acid --v metaphenylenediamlne.

N H l meta-phenylenediamine (Schultz, Farbstofltabellen," 7th edition volume I, No. 62!.)

(obtainable by condensing 4,4'-dianiinodipbenylurea-3,3'-disulionle acid with 2 moles ol i-nitrobenzoyichloride, reducing-and coupling the tetrazotlzed compound with 2 H1015 TIntll-Gd with chromium fluoride: golden yellow.

Treated with chromium fluoride: olden orange.

Treated with chromium fluoride: olden yellow.

Treated with chromium fluoride: yellow. Tmted with chromium fluoride: yellowilh- Treated with copper suliate: brown.

Treated with chromium fluoride or copper sulfate: black.

,Treated with chromium iluorldez golden yellow.

gag 1-(3'-aminophenyl)-5-pyrezolone-3-carboxylic acid; cl. German patent specification Parent component mm. o: the am mad with 1mm l-jmino-Hly 35 l-umixiwmphthoi (obtainable by oou l uni?! 1 with l-( mu o-group. m eon it with l-(3'- MEL 0! N-CHI Tmhd with chromium fluoride: red.

Slade of the dyeing. treoudwitii metal salts,

on poll/Mu! xymhhthuleno-Hulionio acid -b Clove! acid Treated with tasaium bichromato: blackl hydroxynuphthaleue-o-mlioniowid. F p0 audio] the dyeing, mated with metal mus.

(mummy: I

diuotized 1-(4'-nitrobenzoylumlno)Minobenzene-ii-eulionic nyl)-3-methyl-6-pyrazoiona, reducing the nitro-grou the gminomonmzo-dyaatufl thus obi;

ymzoione-a-carboxyllc acid). q

' Treated with chfomium fluoride or potassium blchmmote: reddish black, v

Treated with chromiumjuoride: golden inodiphenyl-2,2'-d Treated with chromiumfluoride: golden v carboxylic acid. '6 yellow. i l il l odlplionylether-fiuiionio acid =8 1-'(3'-uminopbgnyi)-5-pyruoione-3-- Do. 4

our xy oac o I 4,-4'-dhmlnodlphenyl-3,3'-disultonio gold :8 l-qootooiaetylumino-l uminobenuue Treotpd with chromium fluoride: yellow.

nltlkon mixture! wool and Artificial silk with potuulum biohgomatez brown.

amrror Parent component l Bhadeoithed" ,treatedwithmetal stilts onmixtureso woolsndsrtiilelalsilk stapleilber p into the aceto-ecetylamin laminodipheny group to the-amlno-gmup). i

' grnmoicmcooni btainabl b 1' Idlaeotired 1- 4'nitmbenso lamina minimum-tenuous I s lami i-la' 'ii'iln 'iianyn io iuwiii; nilngthe'aminobox or Datidicduqinstheni I tothssminogrnup).

' (obtainable by con i I 2 mols'ol diaeotised i-nitro-l-ainlnchensene Mali-1%.; 2,1-disulionie and reducing the m with l mini 4 i'-bistro-gmups 1mm with chromium smut:

Treated with chromium fluoride: yellow.

7 We claim:

lfA process of producing'i'ast Edyeings which comprises a lying to the fiber a compound or lthefgroup co isting of the aromatic and heteroeyclic series which contains in the molecule anamino group capable oi being diaa'otized. and in addition thereto a membe mnejm n consisting oiwamino and hydroxyl groups. but is free ings which comprises applying to mixtures wool and artiilcial silk staple nberthe watersolu- -ble am dycstufl l-amino-c-hydroxynaphth'alene- 1y to .1. treatment with an agent yielding a metal. 5. A process of producing-rest blue-black dyeirom a grouping capable of forming a metal complex compound/thendiazotizing on the iiberj and subjecting the dyeing. to an alkaline treatment and subsequently to a treatment with an agent yielding a metal.

2. A process of producing last black dyeings which comprises applying to the fiber the.waterdroxynaphthalene-l-sulionic 'acid, thein dialortizing on the fiber and subjecting the dyeingto an alkaline treatment and subsequently to a treatment with an agent yielding chromium.'

8. A process of producin'g'iast brown. dyelngs which comprises applying to the ilber" the water;-

-solubledyestui! l-amino-ii-hydroxynaphe thalene-T-sulionic acid-*Cleves acid-+Cleve's acid, then diazotizing onthe ilb'er and subjecting solublejazo dyestui! I-amino-b-hydroxynaphthalene-I-sulionic acid- Cleves acid- 2-amino-8-h7- droxynaphthalene-c sulionic acid, then dialothing on the fiber and subjecting the dyeing to an alkaline treatment and subsequently to a treatment with an agent yielding a metal.

8. A'PI'OCGSI of producing iastlblack dyeings which comprises applying to mixturesjo! wgol and artificial-silk staple iiber the watersoluble azo dyeetufl l-amino-ii-hydrokyna hthaleneflsulionic acid- Cleves acid-' z amin'o-e-hydroxynaphthalene-il-sulionic acid, then diasotisingcn the fiber and subjecting the dyeing to an alkaline,

i treatment and subsequently .to a treatment withan agent yielding chromium.

4. a process of producing ia'st blue-black e e; v ings which. comprises applying to the fiber the 'naphtha'lene-7-sultonic acid-rCleves acid- '2-.

amino 5 hydrcxynaphtalenefle-sulionic, acid, H thendiasotizing on the ilber and subjecting the an'alkaline treatment andjsubeeq'uent- 7g the dyeingt'o an alkaline treatment and subseq iently to a treatment with an agent .yieldinga metal. 71

"I. A process of producing inst brown drama! which comprises applyin'g to mixtures of wool nd artificial-silk staple fiber. the watersoluble' aeo dyestuils l-amino-iS-hydroWPhthaIene-W- sulfpnic acid- Cleve's acid- Cleves acid, thendiazotizing on the flber and subiectins meaning to an alkaline treatment andsubs'equentlytd a treatment with an agent yielding chromium- 8. Fiber dyed witha-dy'estu'i! by the process claimedinclaiml. v M a v fl l 'iber dyed with a dyestufl'by' the process claimed in claim'z. v 10. Fiber. M d with a dyestuii. by theprocess' claimed in claim 4.

11,1"iber'dyed with 'adyestufl-"by the process claimedlnclaim-8.-=' Y" wmmm WALTER 01mm. i 

